THE  PREPARATION  OF  RENZO 
DIOXANS 


HY 


ARTHUR  WILLIAM  SLOAN 


THESIS 


FOR  THE 


DEGREE  OF  BACHELOR  OF  SCIENCE 


CHEMISTRY 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 


UNIVERSITY  OF  ILLINOIS 


1922 


■ 


ACKNOWLEDGMENT 


The  author  wishes  to  extend  his  sincere  thanks  to 


Dr.  Roger  Adams,  who  suggested,  and  has  criticised 
and  supervised  all  the  work  of  this  problem. 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/preparationofbenOOsloa 


(i) 


TABLE  OP  CONTENTS 

Page 

I*  Introduction 1 

II.  Historical  Part S 

III.  Theoretical  Part 3-5 

IY.  Experimental  Part 
Preparation  of: 

(1)  5,  6 p-bromobenzo , 2-phenyl,  1,  3 dioxan 6 

(2)  5,  6 p-brombenzo,  2-p-bromphenyl , 1,  3-dioxan.  . . .7 

(3)  5,  6 p-brombenzo,  2-p-ohlorphenyl,  1,  3-dioxan.  . . 8 

(4)  5,  6 p-brombenzo,  2-  p phenylethylene , 1,  3-dioxan. 8-9 

(5)  5,  6 benzo,  2-/3 phenylethylene,  1,  3 dioxan  ....  9 

(6)  5,  6 p-nitrobenzo , 2-p-bromphenyl,  1,  3-dioxan  . . 10 

(7)  5,  6 p-nitrobenzo,  2-p-chlorphenyl,  1,  3-dioxan.  . 10 

(8)  5,  6 p-nitrobenzo,  2- [3  phenylethylene,  1,  3-dioxan  11 

(9)  5,  6 p-methylbenzo , 2-phenyl,  1,  3-dioxan  ....  12 

(10)  5,  6 p-methyl,  o-methoxybenzo , 2-phenol,  1,  3 

dioxan 12 

(11)  5,  6 benzo,  2-propyl,  1,  3-dioxan 13-14 

(12)  5,  6 benzo,  1,  3-dioxan 14-15 

(13)  Homosaligenin 15-16 

(14)  p-brom8aligenin 16 

(15)  Butyl  aldehyde 16-17 

V.  Bibliography 18 


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(1) 


PART  I 

INTRODUCTION 


The  dioxans  are  a class  of  compounds  of  comparatively  recent 
origin.  They  are  six  membered  rings  in  which  there  are  four  carbon 
atoms  and  two  oxygen  atoms.  Three  types  are  possible: 


</S> 


yc  x 

c o 

1 

II 


n 

cv  c 

III 


of  which  only  members  of  types  II  and  III  are  known  at  present. 

Kreger2,  in  his  work  on  the  structure  of  disalicyl  aldehyde, 
found  that  saligenin  would  react  with  benzaldehyde  to  give  a compound 
having  properties  entirely  similar  to  those  of  disalicyl  aldehyde. 
Prom  this,  he  was  led  to  prepare  compounds  from  saligenin  and 
p-chlorbenzaldehyde , p-brombenzaldehyde , and  p-nitrobenzaldehyde . 

These  compounds  he  showed  to  be  of  the  type  , the  reaction 

being:  _ . 

4 i X ^ (5’6  Be71550’  2-phenyl^ 

° Q 1,3  dioxan. ) 


0CHrOH  „ 


OH  + v'c 
H' 


‘k 

OMWoje 

H 


The  discovery  of  the  reaction  between  benzaldehyde  and  sali- 
genin has  led  to  the  work  in  this  paper  in  which  it  was  proposed  to 
study  the  reactions  of  substituted  saligenins  with  substituted 
benzaldehydes  to  see  if  the  reaction  were  a general  one,  to  determine 
the  effect  of  substituting  groups  on  the  reaction,  and  to  see  if 
aliphatic  aldehydes  could  be  made  to  condense  with  saligenin  in  a 
manner  similar  to  that  of  aromatic  aldehydes. 


(2) 


PART  II 

HISTORICAL  PART 

Henry3,  in  1902,  seems  to  be  among  the  first  to  have  prepared 
a dioxan.  His  was  the  1,  3-dioxan  i 1 ° which  he  called  tri- 
methylene  methylal.  It  was  made  by  treating  trimethylene  glycol 
with  formaldehyde.  Clarke4,  in  1912,  prepared  the  same  compound  by 
treating  trimethylene  glycol  with  polyoxymethylene  in  the  presence 


C Hj'CHi 


of  orthophosphoric  acid.  He  also  prepared  the  1,  4-dioxan  ih;i 
by  the  method  of  Paworsky^,  dehydrating  ethylene  glycol  with  sulfuric 
acid. 

Members  of  the  benzo  dioxans  have  been  prepared  by  Borsche  and 
Berkhout^  by  using  substituted  phenols  instead  of  glycols,  in  the 
presence  of  dilute  sulfuric  acid.  By  this  method,  Borsche  and  Berk- 
hout  have  been  able  to  prepare*.  A 
(Y“>. 

C"1  CM.  c L Hv  c H-w 


i ii  in  rv  v 

They  attempted  to  confirm  the  structure  of  I by  making  it  from 
p-nitro  saligenin  and  formaldehyde,  but  failed  because  they  could 
not  make  pure  p-nitro  saligenin,  a compound  up  to  that  time  unknown. 

Quite  recently,  Prins7  has  discovered  another  way  to  make 
1,  3-dioxans,  namely,  by  a reaction  between  unsaturated  compounds  and 
formaldehyde  in  the  presence  of  sulfuric  acid,  using  acetic  acid  as 
the  solvent.  Prom  styrolene,  anethol  and  isosafrol,  he  gets  respec- 
tively : 


<Z>  CH-CH, 

O c ►‘x. 


chj0Och-ch-ch3  or  ch3 o<c>  ch  - ch  ch}  } 

O CHV  CM-  ° 


« \ 
CH,  — O 


'*■  I 


O 


and 


or  C^X) 

O CHX  CHi  6 


I 

CH 
l 

C*x~  6 


O - CH, 


■J 


. 


. 

(3) 


PART  III 

THEORETICAL  PART 

Some  of  the  reactions  between  saligenin  and  substituted  ben- 
zaldehydes  go  with  the  greatest  ease,  the  saligenin  and  aldehyde 
merely  being  heated  on  the  steam  bath  until  they  melt  together,  and 
then  allowing  them  to  cool  for  several  hours,  to  solidify.  In  using 
benzaldehyde  and  nitrobenzaldehyde , some  benzoic  acid  should  be 
used  as  a catalyst,  and  for  these  two  aldehydes,  longer  heating  on 
the  steam  bath  is  necessary. 

Prom  the  foregoing,  there  is  every  reason  to  believe  that 
substituted  saligenins  should  give  compounds  with  substituted  ben- 
zaldehydes,  or  other  aromatic  aldehydes,  the  ease  of  formation 
depending  possibly  upon  the  substituting  groups  present. 

It  was  found  that  p-brom  saligenin  could  be  condensed  with 
benzaldehyde,  p-brom  benzaldehyde,  p-chlorbenzaldehyde , and  cinnamic 
aldehyde;  and  p-nitro  saligenin  could  be  condensed  with  cinnamic 
aldehyde.  P-nitro  saligenin  seemed  to  give  mostly  resin  with  p-chlor- 
benzaldehyde and  p-brombenzaldehyde , but  certain  precautions  in 
manipulation  might  give  these  condensation  products.  An  attempt  to 
condense  homo saligenin  with  benzaldehyde  was  unsuccessful;  so  also 
was  an  attempt  to  condense  o,  o-dimethoxy  p-cresol  with  benzaldehyde. 
With  cinnamic  aldehyde,  tho  it  could  be  condensed  with  p-brom  sali- 
genin and  p-nitro  saligenin,  it  could  not  be  condensed  with  saligenin 
itself. 

Since  saligenin  will  condense  with  aromatic  aldehydes,  there 
is  some  reason  to  believe  that  it  will  condense  with  aliphatic 
aldehydes  as  well.  However,  it  may  be  that  a different  type  of 


(4) 


reaction  is  necessary  to  get  the  desired  products.  Borsche  and  Berk- 
£ 

hout°  prepared  5,  6-p-nitrobenzo , 1,  3-dioxan  by  a reaction  between 
40 % formaldehyde  and  p-nitrophenol , in  the  presence  of  dilute  sulfuric 
acid.  They  explain  the  reaction: 


* CH,0 


0aN/\cMxOH 


•OH 


CHiO  y 


Theoretically,  it  should  be  possible  to  use  phenol  and  formaldehyde 
in  a similar  reaction  and  get  5,  6-benzo-l,  3-dioxan,  but  bakelite 
resins  form  so  easily  that  practically  the  reaction  might  not  go. 

3 

Voorhout  , in  his  study  of  the  condensation  products  of  phenol  with 
formaldehyde  in  the  presence  of  dilute  sulfuric  acid  was  able  to 
isolate  only  dioxydiphenylme thane  and  some  of  its  polymers. 

Since  dioxans  are  acetals,  there  is  the  possibility  of  making 
them  by  the  use  of  the  acetal  reaction.  An  attempt  to  condense 

Q 

saligenin  and  formaldehyde,  lasing  Fischer  and  Glebe1 s method  where 
CaOlg  is  used  as  a dehydrating  agent,  gave  no  product.  The  reaction 
should  have  been  tried  with  ZnOlg  as  a catalyst,  or  by  using  dry 
benzene  or  ether  as  the  solvent  for  the  formaldehyde,  but  these 
attempts  were  not  made. 

Using  the  general  reaction  for  condensing  saligenin  with 
benzaldehyde , efforts  were  made  to  get  butyl  aldehyde  to  condense 
with  saligenin;  but  tho  dilute  and  concentrated  hydrochloric  acid, 
dilute  sulfuric  acid,  and  benzoic  acid  were  used  in  various  trials 
as  catylysts,  and  a trial  was  made  without  any  catalyst,  no  product 
of  proved  structure  could  be  obtained,  altho  in  all  cases  except  the 
latter,  where  no  catalyst  was  used,  a practically  colorless  oil  was 
obtained.  This  oil  formed  immediately  in  the  presence  of  mineral 
acids,  but  only  during  several  hours  heating  in  the  steam  bath,  in 


■ 


■ 


. 


. 

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(5) 

the  presence  of  benzoic  acid,  and  not  at  all  in  the  absence  of  cat- 
alysts. It  boiled  all  the  way  from  70°  to  180°C.,  giving  a fair 
fraction  at  167°C.  Comparing  the  5,  6-p-nitrobenzo  - 1,  3-dioxan 
prepared  by  Borsche  and  Berlchout6,  a solid  melting  at  144°-145°,  one 
would  expect  the  condensation  product  of  saligenin  with  butyl 
aldehyde,  5,  6-benzo,  2-propyl,  1,  3-dioxan,  to  be  a solid  at  room 
temperature.  The  oil  actually  obtained  would  not  solidify  even  in 
an  ice  salt  mixture. 


(6) 

PART  IV 

EXPERIMENTAL  PART 

Preparation  of  5,  6-p-brombenzo , 2-phenyl,  1,3-dioxan. 

2 g.  (I  mol)  p-bromsaligenin  and  1 g.  (1  mol)  benzaldehyde 
were  mixed  in  a 200  cc.  round  bottomed  flask  fitted  with  a reflux 
condensing  tube  and  heated  on  the  steam  bath  for  20  minutes.  The 
flash  was  then  allowed  to  stand  at  room  temperature  for  3 hours, 
during  which  time,  the  liquid  solidified  to  a crystalline  mass.  This 
was  broken  up  with  a stirring  rod,  and  50  cc.  of  10$  NaCOg  sol.  were 
added.  After  thoro  shaking,  the  insoluble  product  was  filtered  off 
and  washed  with  water.  It  was  then  crystallized  by  dissolving  in 
35  cc.  hot  95$  alcohol,  adding  water  until  the  solution  became 
milky,  heating  until  clear,  then  allowing  the  solution  to  stand  at 
room  temperature.  By  the  end  of  a half  hour,  a white  crystalline 
precipitate  had  separated  out.  The  mixture  was  cooled  in  an  ice 
bath  filtered.  Yield  1.5  g.  Evaporation  of  the  filtrate  and 
recrystallization  of  the  residue  from  a few  cc.  of  alcohol  gave  0.3g. 
additional  product.  Yield  60$.  M.P.  82°  - 83°.  Recrystallization 
from  95$  alcohol  raised  the  melting  point  to  83°-84°. 

Repeated  trials  using  benzoic  acid  as  a catalyst  did  not  seem 
to  affect  the  reaction  or  the  yields. 

The  product  is  quite  soluble  in  alcohol  and  some  of  it  is 
lost  during  crystallization. 

Analysis  - 

Substance:  0.5000  g. 

Calc,  for  Cl4Hn02Br:  C - 0.2887  g. 

Pound:  0.2900  g. 


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(7) 


Analysis  ( Cont.) 

Pound:  650.1  cc.  of  COg  at  741.0  mm.  and  31.5°C.  collected 
over  water. 

Wt.  C per  cc.  of  CO2  - 0.4461  mg. 

Preparation  of  5 , 6-p-brombenzo , 2-p-bromphenyl,  1,  3 dioxan. 

2 g.  (1  mol)  of  p-brom  saligenin  and  1.8  g.  (1  mol)  p-brom- 
benzaldehyde  were  mixed  together  and  heated  on  the  steam  bath  for  5 
minutes.  The  mixture,  which  at  first  melted  down  somewhat,  soon 
became  a solid  mass.  It  was  allowed  to  stand  at  room  temperature  for 
10  minutes.,  then  100  cc.  of  10$  Na2C03  solution  were  added.  After 
stirring  well,  the  insoluble  product  was  filtered  off  and  washed  with 
water.  Yieldcrude  product  3.2  g. , 89$.  It  was  not  entirely  soluble 
in  60  cc.  of  hot  alcohol,  but  without  filtering  the  solution,  water 
was  added  until  it  became  milky,  and  the  mixture  allowed  to  cool  at 
room  temperature  for  several  hours.  A mass  of  flaky  white  crystals 
separated  out.  These  were  filtered  and  washed  with  95$  alcohol. 

Yield  2.3  g.  M.P.  140°-142.5°.  Recrystallization  from  95$  elcohol, 
filtering  off  the  insoluble  matter,  gave  a M.P.  141°-142°. 

Analysis:  - 

Substance:  0.5000  g. 

Calc,  for  C^H^OgBrg  : 0 - 0.2271  g. 

Pound:  C - 0.2252  g. 

506.8  cc.  of  CC^  at  738.5  mm.  and  31.5°  collected  over 
water. 

Wt.  G per  cc.  of  CO2  - 0.  4444  mg. 


. 


. 


(8) 


Preparation  of  5, 6-p-brombenzo , 2 p-chlorphenyl,  1,3-dioxan . 

2 g.  ( 1 mol)  p-bromsaligenin  and  1.4  g.  (mol)  p-chlor 
benzaldehyde  were  mixed  and  heated  on  the  steam  hath  for  5 minutes. 
The  mass  at  first  melted  do wn  somewhat  and  then  solidified.  It  was 
allowed  to  stand  at  room  temperature  for  30  minutes,  and  then  100  cc. 
of  10$  UagOOg  solution  were  added.  The  insoluble  product  was  broken 
up  with  a stirring  rod,  filtered  off  and  washed  with  water.  Yield 
crude  product  2.9  g. , 91$.  It  was  not  entirely  soluble  in  60  cc.  of 
alcohol,  but  without  filtering,  water  was  added  until  the  solution 
became  milky,  heat  applied  until  it  was  clear,  and  the  resulting 
solution  allowed  to  stand  at  room  temperature  several  hours.  The 
crystals  formed  were  filtered  off  and  washed  with  95$  alcohol. 

Yield  2.3  g.  M.P.  144.5  - 146°.  Recrystallization  from  95$  alcohol, 
filtering  off  the  insoluble  portion,  gave  a M.P.  145°-146°  0. 

Analysis:  - 

Substance:  0.5000  g. 

Oalc.  for  C^H^oOgClBr  : 0 - 0.2581  g. 

Pound:  C - 0.2591  g. 

584.4  cc.  of  COg  at  741  mm.  and  32.5°  0.  collected 
over  water. 

Wt.  0 per  cc.  of  00g  = 0.4433  mg. 

P- 

Preparation  of  5, 6-.brombenzo , 2-  f3  phenylethylene  , 1,3-dioxan . 

2 g.  (1  mol)  p-bromsaligenin  and  1.3  g.  (1  mol)  of  cinnamic 
aldehyde  were  mixed  and  heated  on  the  steam  bath  for  15  minutes. 

A uniform  melt  resulted.  It  was  allowed  to  stand  at  room  temperature 
for  2 hour s , during  which  time,  it  largely  solidified.  The  mass  was 
broken  up  and  100  cc.  of  10$  Nag  CO^  solution  added.  The  insoluble 


i i 

. 


C 


(9) 


product  was  filtered  off  and  washed  with  water.  Yield  crude  product 
1.9  g. , 61 $.  This  was  entirely  soluble  in  30  cc.  hot  95$  alcohol. 
Water  was  added  until  the  solution  became  milky,  heat  applied  to  get 
a clear  solution,  and  the  latter  allowed  to  stand. at  room  temperature 
for  several  hours.  The  white,  flaky,  crystals  which  formed  were 
filtered  off  and  washed  with  95$  alcohol.  Yield  1.0  g.  M.P.  115°r 
118°.  Recrystallization  from  95$  alcohol  gave  a M.P.  118°-120°. 

Analysis  - 

. 

Substance:  0.4000  g. 

Calc,  for  Cl6%302Br  : ® ~ 0.2423  g. 

Pound:  C - 0.2430  g. 

537.2  oc.  of  COg  at  741.2  mm.  and  29.3°  C.  collected 
over  water. 

Wt.  of  C per  cc.  COg  = 0.4522  mg. 

Preparation  of  5,6-benzo,  2- phenylethylene,  1,  3-dioxan. 

2 g.  (1  mol)  of  saligenin  and  2.2  g.  (1  mol)  of  cinnamic  alde- 
hyde were  mixed  and  heated  on  the  steam  bath  for  10  minutes.  Complete 
solution  resulted.  It  did  not  solidify,  however,  on  two  days  stand- 
ing at  room  temperature.  50  cc.  of  10$  NagC03  solution  were  added, 
without  any  apparent  change  in  the  viscous  liquid. 

When  the  NagC03  solution  was  separated  off  and  neutralized 
with  acetic  acid,  a large  part  of  the  saligenin  was  recovered,  show- 
ing that  no  reaction  had  taken  place. 

The  experiment  was  repeated  using  benzoic  acid  as  a catalyst 
and  allowing  the  mixture  to  remain  on  the  steam  bath  for  4 hours, 
but  there  was  no  difference  in  the  result. 


, 

. ... 


(10) 


Preparation  of  5, 6-p-nitrobenzo , 2-p-brompfaenyl,  1,3-dioxan. 

1 g.  (1  mol)  p-nitro  saligenin^  and  1.1  g.  (1  mol)  p-brom- 
benzaldehyde , and  0.25  g.  of  benzoic  acid  were  well  mixed  and  heated 
on  the  steam  bath  for  5 minutes.  One  minute's  additional  heating 
over  a very  small  flame  was  necessary  to  cause  complete  solution. 

The  melt  was  allowed  to  stand  for  15  hours  at  room  temperature.  No 
reaction  seemed  to  have  taken  place  so  the  mixture  was  again  melted 
over  a small  flame  and  heated  for  3 hours.  Too  much  heat  was  used 
however,  and  a small  amount  of  charring  occurred  on  one  side  of  the 
flask.  The  melt  was  again  allowed  24  hours  to  solidify.  Then  50  cc. 
of  10$  Na2C03  solution  were  added  and  the  solid  mass  broken  up.  30cc 
of  ether  were  shaken  with  the  mixture  to  extract  the  desired  product, 
but  the  water  insolbule  portion  was  ether  insoluble  also.  The  ether 
extract  on  evaporation  left  only  a small  amount  of  yellow  gummy 
residue.  The  insoluble  substance  was  filtered  off  and  washed  with 
water.  It  was  taken  up  in  10  cc.  of  hot  95$  alcohol  and  precipitated 
by  addition  of  water  to  produce  milkness,  heating  until  the  solution 
became  clear,  then  cooling  in  ice.  The  yellow  flocculent  precipitate 
which  separated  out  changed  mostly  to  a gummy  mass  when  allowed  to 
stand  over  night,  part  of  which  would  not  redissolve  when  heated  with 
more  alcohol.  Reprecipitation  in  the  same  way  as  before  gave  mostly 
the  same  brownish  gum.  If  the  yellow  precipitate  were  the  desired 
product,  it  was  a very  poor  yield.  The  gum  was  probably  a nitrosali- 
genin  resin  formed  as  a result  of  too  much  heating. 

Preparation  of  5,  6-p-nitrobenzo , 2-p-ohlorphenyl , 1,3-dioxan. 

1 g.  (1  mol)  p-nitrosaligenin  and  0.85  g.  (1  mol)  p-chlorben- 
zaldehyde  and  0.25  g.  of  benzoic  acid  were  well  mixed  and  heated  on 

the  steam  bath  for  5 minutes.  Additional  heating  over  a very  small 


' 


* 


(11) 

flame  for  1 minute  was  necessary  to  cause  complete  melting.  Cooling 
for  15  hours  seemed  to  have  produced  no  change,  so  the  mixture  was 
again  heated  over  a small  flame  for  3 hours,  then  allowed  to  stand 
a day  at  room  temperature.  The  solid  mass  which  had  formed  was 
■broken  up  with  a stirring  rod.  50  cc.  of  10#  Fa2C03  solution  were 
added,  and  after  shaking,  the  insoluble  product  was  filtered  off  and 
washed  with  water.  Yield  crude  product,  1.6 g.  It  was  entirely 
soluble  in  15  cc.  of  hot  95#  alcohol,  but  came  down  as  a yellow 
flocculent  precipitate  when  chilled  in  ice.  Upon  standing,  however, 
it  soon  changed  to  a gammy  mass,  which  was  not  entirely  soluble  when 
reheated  with  alcohol.  The  soluble  portion  was  reprecipitated  by 
by  addition  of  water  to  the  alcohol  solution,  cooling  to  room  temper- 
ature for  1 hour.  Again,  most  of  the  flocculent  precipitate  changed 
to  a brown  gum.  Lack  of  p-nitrosaligenin  to  repeat  the  experiment 
prevented  the  identification  of  this  yellow  precipitate  as  the 
desired  product. 

Preparation  of  5, 6-p-nitrobenzo , 2-/#  phenylethylene  1,  3 
dioxan.  1 g.  (1  mol)  p-nitro  saligenin  and  0.8  g.  (1  mol)  cinnamic 
aldehyde,  and  0.25  g.  of  benzoic  acid  were  w&l  mixed  and  heated  on 
the  steam  bath  for  10  minutes.  Complete  melting  resulted.  After 
standing  for  15  hours  at  room  temperature,  the  aldehyde  appeared  to 
be  still  unreacted,  so  the  mixture  was  again  heated  on  the  steam 
bath  for  3 hours,  and  let  stand  at  room  temperature  for  a day.  50  cc 
of  10#  NagCO^  solution  were  added,  and  the  insoluble  product  filtered 
off  and  washed  with  water.  Yield  crude  product  0.9  g.  This  was 
soluble  in  10  cc.  of  hot  95#  alcohol,  but  gave  no  precipitate  on 
cooling  to  room  temperature.  Addition  of  water  to  the  hot  solution 
and  cooling  to  room  temperature  for  1 hour  brought  down  a soft  yellow 


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(12 ) 

precipitate,  without  the  presence  of  any  gum.  Yield  0.3  g.  M.P. 

135. 5°-136.5°  It  was  not  crystallized  a second  time. 

Analysis- 

Substance  : 0.2000  g.  + 0.3000  g.  Benzoic  Acid. 

Calc,  for  C16H1304lT:  C - 6.1356  g. 
n " C6H5C02H  : C - 0.2066  g. 

Total  C - 0.3422  g. 

Found:  Total  0 - 0.3141  g. 

698.8  cc.  of  COg  at  741.2  mm.  and  30.3°0  collected 
over  water. 

Wt.  of  C per  cc.  of  CO2  = 0.4495  g. 

Preparation  of  5,6  p-methylbenzo , 2-phenyl,  1,  3-dioxan. 

1 g.  (1  mol)  homosaligenin  ( M.P.  98°-101°;  Of.  p. /J  this  paper 
and  0.8  g.  (1  mol)  benzaldehyde  were  mixed  and  heated  on  the  steam 
hath  for  10  minutes.  Complete  melting  resulted.  The  mixture  was 
allowed  to  stand  at  room  temperature  for  two  days,  during  which  time, 
it  did  not  solidify.  50  cc.  of  10$  sol.  FagQOg  were  added,  hut  there 
was  no  apparent  change  in  the  original  substances.  Evidently,  the 
desired  product  was  not  obtained. 

Preparation  of  5,  6 p-methyl-o-methoxybenzo , 2-phenyl,  1,  3-dioxan 
2 g.  (1  mol)  of  0,  o-dimethoxy  p-cresol  ( M.P.  127°-128°; 
prepared  by  Auwer's  method;  Cf.  preparation  of  homosaligenin  , 
p,  1 5 this  paper)  and  1.3  g (1  mol)  of  bengaldehyde  were  mixed  and 
heated  on  the  steam  bath  for  2 hours.  The  melt  was  allowed  to  stand 
for  two  days  at  room  temperature,  but  it  did  not  solidify.  50  cc. 
of  10$  NagCOg  sol.  were  added,  but  the  original  substances  seemed  to 

be  unchanged.  Evidently  the  desired  product  was  not  obtained. 


■ 


(13) 


Preparation  of  5,  6 benzo , 2-propyl,  1,  3-dioxan . 

7 g.  (1.3  mol)  of  butyl  aldehyde  were  saturated  with  benzoio 
acid  (1  g.  ) at  room  temperature,  and  to  this  solution,  10  g.  (1  mol) 
of  saligenin  were  added.  The  resulting  solution  was  heated  at  55°0. 
for  3it  hours,  using  a small  round  bottomed  flask  and  reflux  condense]* 
It  was  allowed  to  stand  11  hours  at  room  temperature,  but  it  did  not 
solidify.  300  cc.  of  5$  NaOH  sol.  were  added,  and  a colorless  oil 
separated  out  and  collected  on  the  surface.  This  was  removed  by 
two  extractions  of  the  mixture  with  100  cc.  of  ether.  The  ether 
extract  was  then  dried  with  CaOlg  and  the  ether  distilled  off  on  the 
steambath  at  50°C.  The  slightly  yellow  liquid  remaining  in  the 
flask  had  a sickening  sweetish  odor.  Yield  crude  product  6.5  g.  It 
boiled,  upon  distilling,  from  70°  to  180°,  the  temperature  remaining 
constant  for  some  time  at  167°,  and  again  at  175°.  The  residue 
left  at  180°  thickened,  and  became  a gummy  mass. 

A repetition  of  the  experiment,  refluxing  the  mixture  for 
4 3/4  hours  at  68°  gave  the  same  product.  It  was  soluble  in  alcohol 
but  could  be  thrown  out  with  water. 

In  another  trial,  dilute  sulfuric  acid  was  used  as  the 
catalyst;  2 g.  (1  mol)  soligenin  and  1.4  g (1.3  mol)  butyl  aldehyde 
were  dissolved  in  10  cc.  of  benzene.  A drop  of  dilute  sulfuric  acid 
was  added,  and  the  solution  shaken  vigorously.  Soon  small  particles 
of  the  yellowish  white  oil  began  to  separate  out. 

Without  a catalyst,  the  reaction  would  not  go.  10  g.  (1  mol) 
saligenin  and  7 g.  (1.3  mol)  butyl  aldehyde  were  mixed  and  refluxed 
at  70°  C.  for  9 hours.  At  the  end  of  this  time,  the  odor  of  butyl 
aldehyde  was  still  present.  After  standing  a week,  100  cc.  of  10$ 

FaoC0„  sol.  were  added,  but  the  insoluble  portion  did  not  seem  to  be 

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the  same  as  that  obtained  in  the  presence  of  a catalyst.  Presumably, 
no  reaction  had  taken  place. 

The  experiment  was  repeated  using  hydrochloric  acid  as  the 

catylyst;  2 g.  (1  mol)  saligenin  were  dissolved  in  1.1  g.  (1  mol) 

butyl  aldehyde,  and  1 drop  of  concentrated  hydrochloric  acid  added. 

An  immediate  reaction  took  place,  with  the  separation  of  a yellowish 

with  sulfuric  acid. 

white  oil,  similar  to  the  oil  obtained  above.  It  would  not  solidify 

A 

when  chilled  in  an  ice  salt  mixture  to  -1°C. 

Preparation  of  5,  6-benzo,  1,  5~dioxan. 

0.2  g.  of  HC1  gas  was  dissolved  in  10  cc.  (0.86  mol)  of 
29%  formaldehyde,  15  g.  (1  mol)  of  saligeni n were  then  added,  and 
the  mixture  heated  over  a small  flame.  A reaction  took  place  quite 
suddenly,  resulting  in  the  entire  solidification  of  the  contents  of 
the  flask  to  a hard,  white,  resinous  mass.  Very  probably,  it  was  a 
resinifioation  product  of  saligenin  formed  due  to  the  presence  of 
hydrochloric  acid. 

Next  a trial  was  run  without  a catalyst.  (Compare  Fischer  and 
Giebe's9  method  for  making  acetals)  10  g.  (1  mol)  saligenin  were 
dissolved  in  20  co.  (2.5  mol)  of  29%  formaldehyde  solution  with 
gentle  heating.  To  remove  all  the  water,  the  solution  was  cooled 
and  14.6  g.  of  CaClg  were  gradually  added.  Then  the  flask  was  stop- 
pered and  allowed  to  stand  40  hours.  By  this  time,  the  odor  of 

formaldehyde  was  entirely  gone.  50  cc.  of  water  were  added  to  the 

in  the  water. 

liquid  mixture,  which  was  entirely  soluble.  By  extraction  with  ether 
4 g.  of  saligenin  were  recovered,  and  the  ether  extract  had  the 
strong  odor  of  formaldehyde.  An  attempt  to  extract  any  reaction 
product  from  the  ether  soluble  residue  with  chloroform  yielded  only 


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a small  amount  of  brown  viscous  liquid,  smelling  strongly  of  formalde- 
hyde. From  all  evidences,  the  desired  reaction  had  not  taken  place. 

Preparation  of  Homosaligenin^ 

! 

22  g.  (1  mol)  sodium  hydroxide  were  dissolved  in  420  cc.  (5 $ 
sol)  of  water.  In  this,  54  g.  (1  mol)  p-eresol  were  dissolved.  Then 
70  cc.  (1.2  mol)  of  29$  formaldehyde  were  added,  the  solution  well 
shaken  and  allowed  to  stand  at  room  temperature  in  a stoppered  bottle. 
By  the  end  of  three  days,  all  odor  of  formaldehyde  was  gone.  The  so- 
lution was  nettralized  (litmus)  with  35  cc.  (1.1  mol)  glacial  acetic 
acid.  This  caused  the  precipitation  of  a large  volume  of  fine  creamy 
product.  Without  filtering  it  off,  300  cc.  of  ether  were  added  and 
shaken  with  the  mixture.  The  solid  product  collected  in  the  ether 
Layer,  but  did  not  dissolve.  (Ether  should  dissolve  homosaligenin  but 
lot  o,  o-dimethoxy,  p-cresol)  The  ether  layer  was  separated  off  and 
bhe  water  solution  again  extracted  with  200  cc.  of  ether.  This  was 
igain  separated  off  and  added  to  the  first  ether  extract,  which  was 
then  filtered  from  the  creamy  precipitate.  This  latter  yielded  49  g. 
rad  gave  a M.P.  90°-95°.  Two  recrystallizations  from  ethyl  acetate 
raised  the  M.P.  to  127°-128°,  but  fc  third  crystallization  had  no  furth  • 
jr  effect.  (o,  o-dimethoxy,  p-cresol  should  melt  at  133°-134°) 

The  ether  filtrate  was  evaporated  to  dryness,  leaving  a bfown- 
.sh  viscous  residue  which  solidified  partly  as  crystals  upon  chilling 
rith  ice.  This  was  crystallized  from  50  cc.  of  chloroform.  The  chlo- 
roform filtrate  upon  evaporation  gave  7 g.  to  8 g.  of  residue  mostly 
3-cresol. 

The  crystallized  product  was  only  partly  soluble  in  75  cc.  of 
hot  chloroform.  The  residue,  2 g.  to  3 g.  had  a M.P.  of  120°-125°. 


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This  second  crystallization  yielded  8.5  g.  of  product  with  a M.P.  of 
91°-92°.  It  was  extracted  twice  with  ether  at  room  temperature, 
filtering  and  evaporating  to  dryness  after  each  extraction,  and  was 
then  recrystallized  from  chloroform.  In  this  way,  2.8  g.  of  product 
melting  at  98°-101°  were  obtained.  (Compare  M.P.  105°  as  given  by 
Auwers)  The  ether  insoluble  residue,  3.3  g. , melted  atl£0°-125°. 

Preparation  of  p-bromsaligenin. 11 

50  g.  (1  mol)  saligenin  were  dissolved  in  1.  of  water,  in 
a 12  1.  flask  and  immersed  in  a tub  of  ice  and  water  to  keep  the 
temperature  between  5°-10°.  The  solution  was  stirred  mechanically 
while  9 1.  of  bromine  water  (containing  65  g.  (1  mol)  bromine)  were 
added  in  the  course  of  1 3/4  hours.  The  solution  was  filtered  to 
free  it  of  a small  amount  of  tar,  and  was  then  extracted  with  3§-  1. 
of  ether,  using  two  extractions.  The  ether  extract  was  dried  over 
CaClg  for  30  minutes,  and  the  ether  was  distilled  off.  A yellow 
liquid  which  solidified  on  cooling  remained.  One  crystallization 
from  benzene  gave  44  g.  of  white,  shining,  plate-like  crystals,  M.P. 
103°-105°.  Evaporation  of  the  benzene  gave  2 g.  of  the  same  product 
56$  yield.  A second  crystallization  of  the  product  from  benzene 
raised  the  M.P.  (Corr.)  to  107°-109°. 

This  product  gave  a blue  color  with  ferric  chloride,  but  no  reel 
color  with  concentrated  sulfuric  acid  as  saligenin  does. 

Preparation  of  Butyl  Aldehyde^2 

A 2 1.  flask  was  fitted  with  a rubber  stopper  carrying  a drop- 
ping funnel,  tube  leading  to  the  bottom  of  the  flask,  outlet  tube  to 
a water  condenser  (120  cm.  long), and  a thermometer.  200  g.  (2.7  mol) 
of  n-butyl  alcohol  were  put  into  the  flask  and  air  bubbled  thru  it 


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slowly.  Then  a mixture  of  144  g.  (0.48  mol)  technical  sodium 
dichromate,  80  cc.  of  concentrated  sulfuric  acid  and  250  cc.  of 
water  were  added  in  not  quite  a solid  stream,  keeping  the  temperatur 
at  90°C.  During  this  addition,  air  was  gently  sucked  thru  the 
apparatus,  hy  attaching  a suction  pump  to  a 500  cc.  suction  filter 
flask  which  was  in  turn  connected  to  the  condenser  with  an  adapter 
glass. 

The  distillate  stopped  coming  over  (at  90°)  before  all  the 
oxidizing  mixture  was  used  up,  sq>  the  reaction  was  stopped.  The 
distillate,  about  300  cc.,  was  separated  from  the  water  layer,  a 
few  cc.  of  aldehyde  recovered  from  the  water  layer  by  salting  out 
with  sodium  chloride,  and  the  aldehyde  fractionated  up  to  85°0.  The 
residue,  about  3 times  the  volume  of  the  distillate,  was  put  back 
into  the  2 1.  flask  with  the  rest  of  the  residue,  heated  to  85°,  a 
small  current  of  air  sucked  thru,  and  the  rest  of  the  dichromate 
run  in  in  rapid  drops.  For  this  last  run,  more  dichromate  solution 
(50  g.  NagCrgOy  2HgO;  85  cc  H2O;  27cc.  cone.  H2SO4  ) was  added. 

The  distillate  was  treated  like  the  first  distillate,  the  two 
fractions  boiling  up  to  85°  being  united.  This  fraction  was  separ- 
ated from  a small  layer  of  water  and  dried  for  15  minutes. over  CaCl2- 

It  was  then  distilled  with  a good  fractionating  column  and  the 

■ 

fraction  boiling  72°-74°  was  collected.  Yield  45  g.  23 $ or  31.7$ 
based  on  a recovery  of  54  g.  of  alcohol. 

The  tarry  material  left  in  the  2 1.  flask  was  discarded,  and 
the  flask  cleaned  with  steam  and  10$  sodium  hydroxide. 


(18) 


PART  V 
BIBLIOGRAPHY 

1.  Meyer  and  Jacobson  - Lehrbuch  der  Organischen  Chemie,  Vol . II, 
Pt.  3,  Ab’t.  3,  p.  1145. 

2.  Kreger,  ,TThe  Structure  of  Disalicyl  Aldehyde  and  the  Formation 
of  Dioxans" , University  of  Illinois  Thesis,  19E2. 

3.  Henry,  Cent.  Bl’t.  1902  II,  929. 

Bui.  Acad.  Roy.  Bel.,  1902,  0.  460. 

4.  Clarke,  Jour,  of  Chem.  Soc.  101,  Pt.  2,  1803  (1912) 

5.  Faworsky,  J.  Russ.  Phys.  Chem.  Soc.  38,  741  (1906) 

6.  Borsche  and  Berkhout,  Ann.  330,  82-107  (1904) 

7.  Prins,  Ch.  Abs.  14,  1119,  1662  (1920) 

Chem.  Weekblad  16,  1510-26  (1919) 

Acad.  Sci.  Amsterdam  22,  51-56  (1919) 

8.  Voorhout,  Ch.  Abs.  14,  1119  (1920) 

9.  Fischer  and  Giebe,  Ber.  30,  3054  (1897) 

10.  Auwers,  Ber.  40,  (2)  2531  (1907) 

11.  Auwers  and  Btlttner,  Ann.  der  Chem.  302,  131,  138  (1898) 

12.  Fosseck,  M.  fiir  C.  2,  614  and  4,  660. 


